Polynitropiperidines



United States 190 5 1 POLYNITROPIPERIDINES Milton B. Frankel, Pasadena, Calif., assigno'r to Aerojet gleliieral Corporation, Azusa, 'Calif., a corporation of o No Drawing. Filed Oct. 3, 1957, Ser. No. 688,808 11 Claims. (Cl. 260-293) This invention relates to new compositions of matter and to their preparation. In particular, the invention relates to polynitropiperidines having the general formula:

wherein R and R are hydrogen or nitro radicals.

This application is a continuation-in-part of my copending US. application Serial No. 392,473, filed Novemoer 16, 1953, now abandoned.

The polynitropiperidines of this invention, such as 3,3,5,S-tetranitmpiperidine, condense with nitro alcohols, such as trinitroethanol, to form highexplosive compounds such as N (2,2,2 tn'nitroethyl) 3,3,5,5 tetranitropiperidine, as more fully disclosed in my copending U.S. application Serial No. 628,949, filed December 12, 1956. Also, the compounds of this invention, such as 3,3,5,5- tetranitropiperidine, react with nitric acid to form onplosive compounds such as N-3,3,5,S-pentanitropiperidine, as more fully disclosed in my copending U.S. application Serial No. 617,668, filed June 25, 1957.

The compounds formed from the polynitropiperidines of the present invention, as taught in the above-mentioned US. applications Serial No. 623,949 and Serial No. 617,- 668, are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162 issued May 17, 1949. One way of using these high explosive compounds in a device such as that disclosed in United States Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The polynitropiperidines of this invention are prepared by condensing ammonium salts of carboxylic acids with polynitro-1,5-pentanediol, in accordance with the general reaction scheme set forth below:

wherein R and R are as defined above and R" is a lower alkyl radical.

To more clearly illustrate my invention, the following example is presented. It is to be understood, however, that this example is intended merely as an illustrative em- Patented Sept. 19, 19%1 bodiment of the invention and it should not be construed as limitative of the scope of said invention in any way.

EXAMPLE Preparation of 3,3,5 ,S-tetranitropiperidine In a l25-ml. Erlenmeyer flask was placed a solution of 4 gm. (0.052 ml.) of ammonium acetate in 40 ml. of water and 4 (0.014 ml.) of 2,2,4,4-tetranitro-1,5- pentanediol. The solution was warmed to 40-50 C. and after several minutes an orange solid separated. The solid was collected and dried to give 2.0 gm. (53.7%) of 3,3,5,5-tetranitropiperidine, M.P. 108-112 C. Recrystallization from isopropyl alcohol gave white needles M.P. 123-127 C.

Analysis.Calcd for C 'H N O' percent C, 22.65; percent H, 2.66; percent N, 26.42. Found: percent C, 23.46; percent H, 2.94; percent N, 26:61.

The polynitro-l,5-pentanediol starting materials for the reaction of this invention, such as the '2,2,4,4-tetra-l,5-

pentanediol of the above example, are readily obtained by reacting an alkali metal or alkaline earth metal salt of polynitrobutanol, such as potassium 2,2,4,4-tetranitrobutanol, with formaldehyde, as more fully disclosed in assignees copending US. application Serial No. 662,550, filed May 29, 1957. g

It is preferred, for reasons of convenience, to conduct the reaction of this invention in an aqueous solution. I have found that optimum results are obtained in the practice of my invention, when an aqueous medium is employed, when the reaction temperature is within the range from about to about 50 0., although higher" or lower reaction temperatures can be employed within the scope of my invention.

It will be appreciated that any of the polynitropiperidines within the scope of my invention can be prepared by the method taught herein. For example, 2,4-dinitro- 1,5-pentanediol and 2,2,4-trinitro-1,5-pentanediol condense with ammonium salts of lower carboxylic acids, such as ammonium formate, ammonium butyrate etc., to yield 3,5-dinitropiperidine and 3,3,5-trinitropiperidine, respectively.

I claim:

1. As compositions of matter, the polynitropiperidines having the formula: 1

wherein R and R are radicals selected from the group consisting of hydrogen and nitro radicals.

2. As a composition of matter, 3,3,5,5-tetrnnitropi peridine having the structural formula: 0iN\ /GE2 /NO 1 V OzN Cg; CH2 N02 3. As a composition of matter, 3,5-dinitropiperidine.

4. As a composition of matter, 3,3,S-trinitropiperidine.

5. The method of preparing polynitropiperidines having the formula:

which comprises condensing at having the formula:

polynitro-1,5-pentanediol with the ammonium salt of a carboxylic acid having the formula: V

9 ll R"-C'ONH4 I wherein R and R are radicals selected from the group lower alkyl radical.

Consisting of hydrogen and nitro radicals and R" is a The method of preparing.polynitropipeiidines having the formula:

wherein R and R are radicals selected from the group consisting of hydrogen and nitro radicals and R" is a lower alkyl radical, at a temperature of from about to about C.

7. The method of preparing 3,3,5,5-tetranitropiperidine which comprises condensing 2,2,4,4-tetranitro-1,5-pentanediol with the ammonium salt of a carhoxylic acid having the formula: i

-"%ONE4 wherein R" is a lower alkyl radical.

8. The method of preparing 3,3,S,5-tetranitropiperidine which comprises condensing 2,2,4,4-tetranitro- 1,5 -pentanediolwith ammonium acetate.

' 9. The method of preparing 3,3,5 ,i-tetranitropiperidine which comprises condensing f2,2,4,4-tetranitro-1,5-pentaue diol with ammonium acetate at a temperature of from about 40 to about 50 C:'

10. The method ofpreparing 3,5-dinitropiperidine which comprises condensing"2,4-dinitro-1,S-pentanediol with the ammonium salt of at earboxylic acid having the formula:

with the ammonium salt of a carboxylic acid having the formula I ll i V B."-C--ONH wherein R" is a lower alkyl radical.

I No references cited. 

1. AS COMPOSITIONS OF MATTER, THE POLYNITROPIPERIDINES HAVING THE FORMULA: 